Polishing agent for copper polishing and polishing method using same
View Patent ↗A polishing agent for copper polishing, comprising (A) an inorganic acid with divalent or greater valence, (B) an amino acid, (C) a protective film-forming agent, (D) an abrasive, (E) an oxidizing agent and (F) water, wherein the content of the component (A) is at least 0.08 mol/kg, the content of the component (B) is at least 0.20 mol/kg, the content of the component (C) is at least 0.02 mol/kg, and either or both of the following conditions (i) and (ii) are satisfied. (i): The proportion of the content of the component (A) with respect to the content of the component (C) is 2.00 or greater. (ii): It further comprises (G) at least one kind selected from among organic acids and their acid anhydrides.
1. A polishing agent for copper polishing, comprising:
(A) 0.08-1.0 mol/kg of a multivalent inorganic acid,
(B) 0.20-2.0 mol/kg of an amino acid,
(C) 0.03-0.3 mol/kg of a protective film-forming agent,
(D) an abrasive,
(E) an oxidizing agent,
(F) water, and
(G) 0.02-1.0 mol/kg of at least one kind selected from among organic acids and their acid anhydrides,
wherein the inorganic acid (A) is one or more selected from sulfuric acid, chromic acid, carbonic acid, hydrogen sulfide, sulfurous acid, thiosulfuric acid, selenic acid, telluric acid, tellurous acid, tungstic acid, phosphonic acid, phosphoric acid, phosphotungstic acid, vanadic acid, silicotungstic acid, pyrophosphoric acid and tripolyphosphoric acid, and
wherein an amount of potassium hydroxide required to increase pH to 4 is at least 0.10 mol per 1 kg of the composition, the pH being of a composition obtained by removing component (G) from the polishing agent for copper polishing.
2. A polishing agent for copper polishing, comprising:
(A) 0.08-1.0 mol/kg of a multivalent inorganic acid,
(B) 0.20-2.0 mol/kg of an amino acid,
(C) 0.03-0.3 mol/kg of a protective film-forming agent,
(D) an abrasive,
(E) an oxidizing agent,
(F) water, and
(G) 0.02-1.0 mol/kg of at least one kind selected from among organic acids and their acid anhydrides,
wherein a proportion of a content of the component (A) with respect to a content of the component (C) is 2.00-12, and
wherein the inorganic acid (A) is one or more selected from sulfuric acid, chromic acid, carbonic acid, hydrogen sulfide, sulfurous acid, thiosulfuric acid, selenic acid, telluric acid, tellurous acid, tungstic acid, phosphonic acid, phosphoric acid, phosphotungstic acid, vanadic acid, silicotungstic acid, pyrophosphoric acid and tripolyphosphoric acid, and
wherein an amount of potassium hydroxide required to increase pH to 4 is at least 0.10 mol per 1 kg of the composition, the pH being of a composition obtained by removing component (G) from the polishing agent for copper polishing.
3. The polishing agent for copper polishing according to claim 1 , wherein the component (G) is at least one kind selected from among organic acids with two carboxyl groups and pKa values of not greater than 2.7, their acid anhydrides, and organic acids with 3 or more carboxyl groups.
4. The polishing agent for copper polishing according to claim 1 , wherein the component (G) is at least one kind selected from among oxalic acid, maleic acid, maleic anhydride, malonic acid and citric acid.
5. The polishing agent for copper polishing according to claim 1 , wherein pH is 1.5-4.0.
6. The polishing agent for copper polishing according to claim 1 , wherein the component (A) is at least one kind selected from among sulfuric acid and phosphoric acid.
7. The polishing agent for copper polishing according to claim 1 , comprising an amino acid with a pKa value of 2-3 as the component (B).
8. The polishing agent for copper polishing according to claim 1 , wherein the component (C) is a triazole compound.
9. The polishing agent for copper polishing according to claim 8 , wherein the triazole compound is at least one kind selected from among benzotriazole and its derivatives.
10. The polishing agent for copper polishing according to claim 1 , wherein the component (D) is at least one kind selected from among colloidal silica and colloidal alumina, and a mean particle size of the component (D) is not greater than 100 nm.
11. The polishing agent for copper polishing according to claim 1 , wherein the component (E) is at least one kind selected from among hydrogen peroxide, persulfuric acid and persulfuric acid salts.
12. A polishing method, comprising polishing a copper-containing metal film using the polishing agent for copper polishing according to claim 1 , to remove at least a portion of the metal film.
13. The polishing method according to claim 12 , wherein a maximum thickness of the metal film is 5 μm or greater.
14. The polishing method according to claim 12 , wherein a maximum thickness of the metal film is 10 μm or greater.
15. The polishing method according to claim 12 , wherein a polishing speed for the metal film is at least 30000 Å/min.
16. The polishing agent for copper polishing according to claim 2 , wherein the component (G) is at least one kind selected from among organic acids with two carboxyl groups and pKa values of not greater than 2.7, their acid anhydrides, and organic acids with 3 or more carboxyl groups.
17. The polishing agent for copper polishing according to claim 2 , wherein the component (G) is at least one kind selected from among oxalic acid, maleic acid, maleic anhydride, malonic acid and citric acid.
18. The polishing agent for copper polishing according to claim 2 , wherein pH is 1.5-4.0.
19. The polishing agent for copper polishing according to claim 2 , wherein the component (A) is at least one kind selected from among sulfuric acid and phosphoric acid.
20. The polishing agent for copper polishing according to claim 2 , comprising an amino acid with a pKa value of 2-3 as the component (B).
21. The polishing agent for copper polishing according to claim 2 , wherein, the component (C) is a triazole compound.
22. The polishing agent for copper polishing according to claim 21 , wherein the triazole compound is at least one kind selected from among benzotriazole and its derivatives.
23. The polishing agent for copper polishing according to claim 2 , wherein the component (D) is at least one kind selected from among colloidal silica and colloidal alumina, and a mean particle size of the component (D) is not greater than 100 nm.
24. The polishing agent for copper polishing according to claim 2 , wherein the component (E) is at least one kind selected from among hydrogen peroxide, persulfuric acid and persulfuric acid salts.
25. A polishing method, comprising polishing a copper-containing metal film using the polishing agent for copper polishing according to claim 2 , to remove at least a portion of the metal film.
26. The polishing method according to claim 25 , wherein a maximum thickness of the metal film is 5 μm or greater.
27. The polishing method according to claim 25 , wherein a maximum thickness of the metal film is 10 μm or greater.
28. The polishing method according to claim 10 , wherein a polishing speed for the metal film is at least 30000 Å/min.
29. The polishing agent for copper polishing according to claim 1 , wherein the inorganic acid (A) is one or more selected from sulfuric acid, carbonic acid, hydrogen sulfide, sulfurous acid, thiosulfuric acid, selenic acid, telluric acid, tellurous acid, phosphonic acid, phosphoric acid, phosphotungstic acid, silicotungstic acid, pyrophosphoric acid and tripolyphosphoric acid.
30. The polishing agent for copper polishing according to claim 2 , wherein the inorganic acid (A) is one or more selected from sulfuric acid, carbonic acid, hydrogen sulfide, sulfurous acid, thiosulfuric acid, selenic acid, telluric acid, tellurous acid, phosphonic acid, phosphoric acid, phosphotungstic acid, silicotungstic acid, pyrophosphoric acid and tripolyphosphoric acid.
31. The polishing agent for copper polishing according to claim 1 , wherein the component (D) is one or more selected from silica, alumina, zirconia, ceria, titania, silicon carbide, polystyrene, polyacryl and polyvinyl chloride.
32. The polishing agent for copper polishing according to claim 2 , wherein the component (D) is one or more selected from silica, alumina, zirconia, ceria, titania, silicon carbide, polystyrene, polyacryl and polyvinyl chloride.
33. The polishing agent for copper polishing according to claim 1 , wherein the inorganic acid (A) is one or more selected from sulfuric acid, chromic acid, carbonic acid, hydrogen sulfide, sulfurous acid, thiosulfuric acid, selenic acid, telluric acid, tellurous acid, tungstic acid, phosphonic acid, phosphoric acid, vanadic acid, pyrophosphoric acid and tripolyphosphoric acid.
34. The polishing agent for copper polishing according to claim 2 , wherein the inorganic acid (A) is one or more selected from sulfuric acid, chromic acid, carbonic acid, hydrogen sulfide, sulfurous acid, thiosulfuric acid, selenic acid, telluric acid, tellurous acid, tungstic acid, phosphonic acid, phosphoric acid, vanadic acid, pyrophosphoric acid and tripolyphosphoric acid.